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Ag 2S quantum dot-sensitized solar cells

Article  in  Electrochemistry Communications · September 2010

DOI: 10.1016/j.elecom.2010.06.006

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 Electrochemistry Communications 12 (2010) 1158–1160

Contents lists available at ScienceDirect

Electrochemistry Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e l e c o m

Ag2S quantum dot-sensitized solar cells

Auttasit Tubtimtae a, Kun-Lun Wu a, Hao-Yu Tung a, Ming-Way Lee a,⁎, Gou Jen Wang b
a
Department of Physics and Institute of Nanoscience, National Chung Hsing University, Taichung, 402, Taiwan
b
Department of Mechanical Engineering and Institute of Biomedical Engineering, National Chung Hsing University, Taichung, 402, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: We present a new photosensitizer – Ag2S quantum dots (QDs) – for solar cells. The QDs were grown by the
Received 1 May 2010 successive ionic layer adsorption and reaction deposition method. The assembled Ag2S-QD solar cells yield a
Received in revised form 2 June 2010 best power conversion efficiency of 1.70% and a short-circuit current of 1.54 mA/cm2 under 10.8% sun. The
Accepted 3 June 2010
solar cells have a maximal external quantum efficiency (EQE) of 50% at λ = 530 nm and an average EQE of
Available online 16 June 2010
∼ 42% over the spectral range of 400–1000 nm. The effective photovoltaic range covers the visible and near-
infrared spectral regions and is ∼ 2–4 times broader than that of the cadmium chalcogenide systems — CdS
Keywords:
Quantum dots
and CdSe. The results show that Ag2S QDs can be used as a highly efficient and broadband sensitizer for solar
Solar cells cells.
Silver sulfide © 2010 Elsevier B.V. All rights reserved.
Successive ionic layer adsorption
Reaction deposition

1. Introduction
Dye-sensitized solar cells (DSCs) are a promising low-cost
alternative to silicon-based solar cells. In 2005 they achieved a
power conversion efficiency of 11.18% [1]. The key component of a
DSC is a photoelectrode consisting of a mesoporous, dye-coated TiO2
film sintered to fluorine-doped tin oxide (FTO) glass. The most
commonly used dyes are the Ru complexes, N3 and N719, which
have large optical absorption in the visible range (400–700 nm), but
small absorption in the infrared. The solar spectrum covers the range
of 0.3–2.5 μm with more than 50% sunlight distributed beyond
700 nm: i.e., more than 50% of the sunlight is wasted by the dye. The
pursuit of alternative broadband light sensitizers to the Ru
complexes has become an active field of research endeavor. One
promising alternative is semiconductor quantum dot (QD) sensiti-
zers, which have several advantages over dye sensitizers such as
tunable energy gaps [2], large absorption coefficients [3], and
multiple electron-hole pair production [4]. Much of the work related
to QD sensitizers has been performed on CdS, CdSe, PbS and PbSe [4–7].
Thin semiconductor absorbers without quantum-size effect have also
been used as sensitizers for solar cells [8,9].
Ag2S is an important material for optoelectronics [10]. It has an
energy gap of Eg ∼ 1.1 eV [11], which is equal to the optimal bandgap
of 1.13 eV for a photovoltaic device [12], suggesting that Ag2S could be
an optimal solar absorber. Vogel et al. briefly investigated the use of
Ag2S QDs as sensitizers, but they did not observe a significant
⁎ Corresponding author.
E-mail address: mwl@phys.nchu.edu.tw (M.-W. Lee).
photovoltaic effect [13]. Reber and Rusek investigated the production
of hydrogen by sunlight with Ag2S-modified CdS powders [14].
In this work we report on the synthesis of Ag2S QDs produced by
successive ionic layer adsorption and reaction deposition (SILAR). The
QDs have been successfully used as a sensitizer for solar cells. We
investigate the dependence of the photovoltaic parameters on the SILAR
cycle, ZnS coating and incident light intensity. The external quantum
efficiency (EQE) spectra reveal an effective photovoltaic range covering
the full visible and near-infrared (NIR) spectral regions.
2. Experimental
2.1. Synthesis of Ag2S QDs
Nanoporous TiO2 films were prepared by spreading a commer-
cial TiO2 paste (Dyesol DSL-18NR-T, diameter ∼ 20 nm) onto FTO
glass (15Ω/□) using the doctor blade method, followed by sintering
at 450 °C for 30 min. The thickness of the TiO2 films, determined
from cross-sectional scanning electron microscopic (SEM) images,
was ∼ 12 μm. Finally, a 3 μm-thick TiO2 light-scattering layer
(diameter ∼ 400 nm) was deposited on top of the electrode.
Ag2S QDs were synthesized using the SILAR method [14]. First, a
0.1 M AgNO3 ethanol solution was prepared by dissolving AgNO3
crystals in ethanol, then stirring vigorously for 30 min. A TiO2
electrode was dipped into the 25 °C AgNO3 solution for 1 min, washed
with ethanol, then dipped into a 0.1 M Na2S methanol solution for
3 min. The two-step procedure forms one SILAR cycle. Samples went
through n SILAR cycles, herein referred to as Ag2S (n). The Ag2S-
coated TiO2 film became darker as the number of SILAR cycles was
increased.

1388-2481/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2010.06.006
 A. Tubtimtae et al. / Electrochemistry Communications 12 (2010) 1158–1160 1159

A ZnS coating on the QDs surface can reduce the surface Table 1
recombination of the photoelectrons. For deposition of the ZnS Photovoltaic data of Ag2S-QD solar cells with different SILAR cycles, ZnS coating and a
scattering layer.
coating, the Ag2S QD-coated TiO2 electrode was dipped into a 0.1 M
zinc acetate ethanol solution for 1 min, then into a 0.1 M Na2S Electrodes Jsc (mA/cm2) Voc (V) FF (%) Efficiency (%)
methanol solution for 1 min. Ag2S (3) 3.7 0.31 38.1 0.43
Ag2S (4) 4.5 0.33 47.4 0.70
2.2. Assembly of QD solar cells Ag2S (5) 3.9 0.36 36.8 0.51
Ag2S (6) 3.6 0.31 29.8 0.33
Ag2S (4)/ZnS 5.7 0.37 36.1 0.76
The Ag2S-sensitized TiO2 electrode and the counterelectrode were Ag2S(4)/scattering layer 7.3 0.33 40.8 0.98
sandwiched using a 190 μm-thick parafilm spacer. The Pt counter- Ag2S(4)/scattering layer/ZnS 4.2 0.35 46.8 0.68
electrode was prepared by dripping a drop of 5 mM H2PtCl6 ethanol
solution onto a FTO glass substrate, followed by heating at 400 °C for
15 min. The polysulfide electrolyte consisted of 0.5 M Na2S, 2 M S, on the TiO2 electrode as the SILAR cycle is increased (or a decreasing
0.2 M KCl and 0.5 M NaOH in methanol/water (7:3 by volume). quantum-size effect due to larger QD sizes).
Table 1 lists the photovoltaic parameters of the Ag2S-QD DSCs with
2.3. Photovoltaic measurements various SILAR cycles. Initially, the short-circuit current density Jsc and
power conversion efficiency η increased with n, but they started to
The absorption spectra were recorded with a Hitachi UV–vis decrease when n exceeded five. The best η is 0.70% for Ag2S(4). The
2800A spectrophotometer. The current–voltage (I–V) characteristics open-circuit voltage Voc is 0.31–0.36 V and is almost independent of n.
were recorded using a Keithley 2400 meter with an Oriel 150 W Xe The coating of a ZnS layer onto the optimal sample Ag2S(4) increased
lamp. An Oriel band pass filter simulated the AM 1.5 spectrum. The η from 0.70 to 0.76 %. The coating of a TiO2 scattering layer onto the
active area of the cell was 0.35 cm × 0.35 cm. The EQE spectra were Ag2S(4) sample produced the largest enhancements of η from 0.70 to
measured using an Acton monochromator with a 250 W tungsten- 0.98% and Jsc from 4.5 to 7.3 mA/cm2. However, when the sample was
halogen lamp. For each experimental condition, a batch of five coated with both a ZnS and a scattering layer, η and Jsc again
samples was prepared and measured. Experiments were repeated decreased. The dependence of η on the n and ZnS coating is probably
three times to ensure the consistency of the data. related to the pore size of the TiO2 electrode. Overcoating to the QDs
decreases the pore size and impedes the flow of the electrolyte,
3. Results and discussion leading to a reduced photocurrent.
Fig. 2 shows the EQE spectra of the Ag2S (4) QD solar cells over the
The inset to Fig. 1 shows a TEM image of a QD-coated TiO2 film spectral range of 350–1100 nm. The EQE spectrum of Ag2S (4) shows a
processed with four SILAR cycles. Many QDs can be clearly observed, broad, pronounced peak over the range of 400–600 nm and a small
distributed randomly over the TiO2 surface. The QDs are well EQE over 600–1100 nm. The EQE over the latter region (600–
separated with no aggregation observed. The average diameter of 1100 nm) is greatly enhanced by a factor of five for the ZnS-coated
the QDs is estimated to be ∼2.5 nm. The areal density of the QDs is sample, indicating that the ZnS coating reduces the photoelectron
∼ 1.3 × 105 particles/μm2. Fig. 1 shows the UV–vis optical absorbance recombination. The spectra have a maximal EQE = 50% at λ = 530 nm
spectra of Ag2S QD-loaded TiO2 electrodes with various SILAR cycles. A and an average EQE = 42% in the NIR range (650–900 nm). The most
broad absorption band covering the whole spectral range appears in important feature is that the Ag2S EQE covers the spectral region of
the QD-loaded samples and the absorption intensity increases with 400–1000 nm, giving an effective range of 600 nm. This is much
the SILAR cycle. The absorption band is characteristic of the high-level broader than that of the cadmium chalcogenide systems: CdS
excitonic excitation absorption of a semiconductor, clearly showing (spectral range: 400–550 nm, effective range ∼ 150 nm) and CdSe
the successful deposition of Ag2S QDs on the TiO2 surface. The peak at (400–700 nm, effective range ∼ 300 nm) [15,16].
∼ 375 nm is due to the fundamental absorption edge of TiO2. The Fig. 3 shows the I–V curves under various light intensities Pin.
absorption spectra are not affected by the ZnS coating. The increasing Table 2 lists the photovoltaic parameters. It can be seen that η
absorption indicates that an increasing amount of QDs are deposited increases from 0.98 to 1.70% – a 70% increase – as Pin is reduced from

Fig. 1. UV–vis absorption spectra of TiO2 electrodes sensitized with various Ag2S QDs.
The labels next to the curves denote the number of SILAR cycles. Inset: TEM micrograph Fig. 2. External quantum efficiency spectra of Ag2S QD-sensitized solar cells prepared
of an Ag2S(4) QD-coated TiO2 film. under various conditions. The lines are guide for the eye.
1160 A. Tubtimtae et al. / Electrochemistry Communications 12 (2010) 1158–1160

Table 2
Photovoltaic data of Ag2S (4) QD-loaded TiO2 electrodes under various sun intensities.
The electrodes were covered with a TiO2 scattering layer.

Jsc (mA/cm2) Voc (V) FF (%) Efficiency (%)

10.8% sun 1.54 0.29 39.7 1.70

40.8% sun 4.18 0.30 46.2 1.41
99.4% sun 7.26 0.33 40.8 0.98

TiO2 and shown that they provide respectable quantum efficiencies over
a wide spectral range and with the potential for high efficiencies.

Fig. 3. Current–voltage curves under various light intensities.
99.4 to 10.8% sun. The increase arises primarily from Jsc, which
produces two times more Jsc per unit light power when Pin is reduced.
The efficiency of 1.70% observed herein is high for QD DSCs, but the
Voc ∼ 0.35 V could be improved. To date, the best Voc for liquid-
junction QD DSCs is 0.6–0.7 V [17,18]. By developing better electro-
lytes, it should be possible to raise the Voc and η.
4. Conclusions
In conclusion, we have demonstrated Ag2S-sensitized liquid-junc-
tion nanoporous solar cells, prepared by SILAR of Ag2S on nanoporous
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